Process for the manufacture of chlorinated derivatives of alphachloroethylbenzene



iatented Oct. 30,1951

PnooEss Fon: '1HE MANUFACTURE OF CHLORINATED. DERIVATIVES F ALPHA ,YCHLOROEIHYLBENZENE r I Eugen Gottfried" Galitzenstein, Wallington, and

-- 'Cyril Woolf, London, England, assignors to The Distillers Company, Limited, Edinburgh, Scotland, a British company N0 Drawing. Application December 3, 1946, Se-

E PATENT] OFFICE rial No.

The present invention is ior improvements'in 'or relating to the manufacture of chlorinated "derivatives of alpha-chlor'o-ethylbenzene. So far as we are-aware, the chlorination of s was. (01; 260-651) 713,'8 53.' In Great Britain December Similarly, reaction of two molecules of chlorine can in addition to or instead of reacting with. the side chain theoretically give rise to the following nuclear chlorination products (again neglectalpha-chloroethyl benzene hasnever been de- '16 m positional isomers): scribed. Attempts which we made to chlorinate it with the aid of the customary chlorination catalysts, such as ferric chloride, antimony pentachloride and the like, failed completely to I 01 furnish the desired results, because these catam (1i lysts caused elimination of hydrogen chloride from the side chain, thus forming styrene with e o the resultant formation of resinous products. According to the present invention there is provided a process for the manufacture --of v). O -OH: chlorinated derivatives of alpha-chloroethyl ben- "z ene which comprises reacting al'pha-chloro- \CHCl ethyl benzene or a nuclear-chlorine substitution 6 product thereof in the liquid phase withgaseous H H01 chlorine at a temperature not exceedin 130 C. C in the presence ofiodine as chlorination catalyst. l The iodine catalyst may be formed in situ in the reaction mixture fronian iodine compounde. g. iodoform or ethyl iodide. '.About-0.12-0.5% of LC s iodine calculated on the alpha-chloroethylbenzene-or the nuclear chlorine substitution product 110 has :been found to give satisfactory results. By 01H $3101 the. process according to the present invention chlorine reacts readily with the alpha-chloro H ethylbenzene or the nuclear chlorine substitution i C1 product thereof and without I any substantial d s on formation of resinous matter as was the case Compounds of the type (ii), (iv) and (v) are wh n using t customary hyd ou m tal hereinafter referred to as chloro-addition comchloride chlorination catalysts. Y I v pounds. 7

Reaction of one molecule of chlorine can in ad- A feature of the invention consists in that the dition to or instead of reacting ,With the, s de chloro-addition compounds are separated from ch theoretically g i e e i ll w 'ng the reaction mixture, and subjected to pyrolytic nuclear Chlorination p o ucts (neglecting p s decomposition to eliminate hydrogen chloride O al i s): from the nucleus. Preferably the pyrolytic (i) CHCLOH; 40 decomposition is effected at a temperature of 180 I to 300 C. preferably at a reduced pressure of 50 to 200 mms. of mercury. HO OH The chlorination process of our invention, can 'HJJ be carried out within a very wide range of temperature. We prefer, however, to carry out the process at temperatures of between 10 and C1 130 G. Since at temperatures below 10 C. the and 7 reaction velocity is slow, whilst above 130 C. un- (a) d desirable side reactions occur. v r I On investigating the process of our invention j we have discovered furthermore that the chlorinatedcompounds resulting from the chlorina-- HO CBC] tion process vary fundamentally according to the r =1 temperatures at which the chlorination process 66 is carried out. By working attemperaturesbe- Exdmple I.A current of chlorine was passed into 787.2 g. (5.27 mols.) of alphachloroethyl- .beezee eet il e 92% p edin .dissolved therein. #:The liquid vvas vigorqusly stirred and other part of the chlorine reacts with the benzenoid ring by simple addition to the double bonds thereof to form lchlordeadditionccomr maintained at C. by external cooling. After .10 hours, 7.817 mols. of chlorine had reacted with the formation of 5.896 mols. of hydrogen pounds. The extent of formationoi thesechloroaddition compounds is diminished at increasing temperatures of chlorination.

When, on the other hand-the chlorinatign ac cording to our invention isparniedmufifit Slim" peratures of between 90 and 130 0., chlorine enters exclusively into the alpha;chloroethy1 si de chain. By chlorinating at inter :i-ie1,te,j;fe pera- Ofsthectotal chlorine which had entered theinucleus', 39% by volume had entered lay-addition The reaction mixture was shaken with-, powdege decolourising carbon to remove l dissolyedi iodinie. jAfter filtering oil the carbon,

It e. chlorinati on product was then slowly dropped einto atheatedstill attached to a short fractionating colygnn. ,A pressure of 90 mm. mercury wasin aintainedgin fthe apparatus, the kettle temtures of between -90 C. mixtures of nuclear-- and side-chain-chlorinated products are iormed.

It is therefore possible by employingtemperatures of between 10: C. and 30 C. durin the echlorinatien ce t btain la ."mixture. of nuc ea hl l' e er e i :ef 1pha.-chl roethy1- b ene Wh ls by orkin .at' 5 01 .30"- 50. 53116-- iret ve pfg a pharehloro thylben ene.;on-of n clear chlorine substitution uproducts lther eof, which are chlorinated in the side chain are produced.

Normal ring-substitution chlorination will give rise to products such. as alpha-chloroethylmonochlorobenzene, alpha chloro ethyl di chlorobenzene and alpha-chloroethyl-trichlorobenzene according to the quantity of chlorine employed.

At the same time, ringchlorinated derivatives of alpha-chloroethyl cyclohexadiene, alphachlcroethyl cyclohexene and alpha-chloroethyl cyclohexane are produced when working within the lower temperaturerangeby simple addition of chlorine to the benzenoid nucleus.

The chlorination of alpha-ch1or0ethylbenzene in accordance with this invention may be carried out in the presenceof solvents which are inert to the action of chlorine. The use of a polar solvent, such as nitrobenzene, reduces the extent of the chloro-addition reaction.

After completion ofthe chlorination process, the iodine may be removed from the reaction product in any convenientmanner, for instance by the action of powdered activated charcoal or sodium thiosulphate.

The unchanged alphachloroethylbenzene and its lower substitution products such as alphaehlereethyl zm eeeh er n e an al h chloroethyl dichlorobenzene produced by -chlorinating at temperatures of 10 to 30 0. maybe separated one i rom the other and ;fro m the chlormaddition compounds and higher substituted chlorination products by 7 fractional distillation at reduced pressure.

We have feund a the ehloroead iti co pounds revert to. the henzenoid structure onheatme t m at res-b tw en .1 e39 C. prefer.- ably at pressures of -200;mrn. mercury,- as a result of the elimination ;of -hydrogen;chlor ide ite t nu eu oi tthe chlorod t compounds. There is also a partial eliminationu-of h e chlorid from t zalpha-chloroethy up f a phareh r ethv e richlorobenzen and higher .chlorosubstituted derivatives of .alpha: chloroethylbenzene which may be;presen t in ith reaction mixture or formed during thepyrglytic ees ethe ewieesla ed I perature beir -ig kept at 220 to 250 C. The liquid was distilled continuously from the kettle togethen-With hydrogen chloride gas, and the rate of feed was adjusted to the same speed as that ,;,of.;d stil1.ation. Al th liquid haddi lle in a thre 1 103- 1 .-.a ;d;;2-. .8 mol of hydreee c l e wereevolved, semelfief r s nremeim zi e: inethel. i1 :Dur-ins .i i lst e som teem- --bi d iodine nWh Gh was mi llyeb u d wa sli era ei audibl was. rem ved f om he-d ti llat zhy.-: ha p wit sd ee ri ne c rb n. h mduqk am n irae ien e .a Him-1 3. z r, nr es.sure- .flh dis i ledl uid ha -.-m e l l r emnqsitio tei re se a pe centa e .eiue rin th lastzee umn 9 .theriell wina ta l chlornethylbenzene were, chlorinated in: thepres- Q1 0 Off-3.13%- cfziodme; until 11.56 1 mols.. of-lchloi- :15, mols.;of hydrogen; chloride hrsand at 30 C. for .aaiurther .3,; hr,s. The-.productwasthentreated as described miEXample I. .The products obtainedcarelset tout inythe followin 1 table, leach expressed as. a molecular -pelfcentage of total products; obtained:

Per cent alpha-chloroethylbenzene ,4.7 A lpha-chloroethyl monochlorobenzene 5.919 Alpha-chloroethyl dichlorobenzene 42,2 A-lpha chloroethyl -trichlorobenzene 520.15 T c o tyre #14223 The process of the invention is also applicable to the chlorinationof the lower nuclear-chlorinated derivatives of alpha-chloroethyl benzene such as the products obtained by the fractionation of the products obtained in the foregoing examples; the following example illustrates the chlorination of these nuclear-chlorinated products:

Example III.424 g. of a mixture consisting of 85.5% alpha-chloroethyl monochlorobenaene and 14.5% of alpha-.chloroethyl-dichlorobenzene were admixed with 0.5 g. iodine and treated with chlorine for five hours at 20 C. 1.154 mols, of chlorine had reacted and 0.74 mol. of hydrogen chloride had been formed. .I -Ience 47.3% of the chlorine entering the nucleus had reacted by addition. The product was then treated as described in Example I, with the following result, expressed as molecular percentages of the total products.

Per cent 56. 2 32. 3 ll. 5

M ols Unchanged alpha-ehloroethyl monochlorobenzene 1.320 A1pha-chloroethyl-dichlorobenzene 0.759 Residue of alpha-chloroethyltrichlorobenzene 0.270

Boiling Yield Fraction point/7 Degrees 85-90 90-110 Residue Grams Dichloroethyl-benzene Trichloroethyl-benzene Higher chlorinated products The first two fractions in the above table, upon treatment with alcoholic potash were converted to side-chain chloro-substituted styrenes which were converted to benzoic acid on oxidation with dichromate, thus demonstrating the absence of nuclear-chlorinated products. The first fraction was found to consist of a mixture of alpha alpha and alpha beta dichloroethylbenzenes, whilst the second fraction was a mixture of alpha-alpha-betaand alpha-beta-beta-trichloroethylbenzenes.

The products obtained by the chlorination process according to our invention are valuable intermediary products for the production of chlorinated styrenes which may be used for the production of polymeric substances.

What we claim is:

1. A process for the manufacture of chlorinated derivatives of alpha-chloroethyl benzene which comprises reacting a benzenoid compound of the class consisting of alpha-chloroethyl benzene and nuclear chlorine substitution products thereof in the liquid phase with gaseous chlorine at a temperature between -10 C. and 30 C in the presence of iodine as chlorination catalyst, the iodine being used in an amount of about 0.12 to 0.5% by weight of said benzenoid compound to produce alpha-chloroethyl benzene products having nuclear chloro substitution and chloro addition groups and converting at least one chloro addition product in the reaction mixture to the corresponding chlorine substituted chloroethyl benzene derivative by heat treatment at a temperature between 180 to 300 C.

2. A process in accordance with claim 1 in which the heat treatment is conducted under a pressure of to 200 mm. of mercury.

3. A process in accordance with claim 1 in which the heat treatment is carried out after removal of unreacted benzenoid compounds of the class mentioned.

4. A process for the manufacture of chlorinated derivatives of alpha-chloroethyl benzene which comprises reacting a benzenoid compound of the class consisting of alpha-chloroethyl benzene and nuclear chlorine substitution products thereof in the liquid phase with gaseous chlorine at a temperature between -10 C. and 30 C. in the presence of iodine as chlorination catalyst, the iodine being used in an amount of about 0.12 to 0.5% by weight of said benzenoid compound to produce alpha-chloroethyl benzene having nuclear chloro substitution and chloro addition groups and feeding the reaction mixture continuously into a zone which is maintained at a temperature between and 300 C. and removing the dehydrohalogenated chloro substituted benzene derivative commensurate with the feed. a

5. A process for the manufacture of chlorinated derivatives of alpha-chloroethyl benzene which comprises heating a chloro addition compound of alpha-chloroethylchlorobenzene at a temperature of 180 to 300 C. and removing hydrochloric acid to produce the corresponding alpha-chloroethyl-chlorobenzene.

6. A process in accordance with claim 5 in which the heating is conducted under a pressure of 150 to 200 mm. of mercury.

EUGEN GOTTFRIED GALITZENS'I'EIN. CYRIL WOOLF.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Levine et al. Mar. 19, 1940 OTHER REFERENCES Number 

1. A PROCESS FOR THE MANUFACTURE OF CHLORINATED DERIVATIVES OF ALPHA-CHLOROETHYL BENZENE WHICH COMPRISES REACTING A BENZENOID COMPOUND OF THE CLASS CONSISTING OF ALPHA-CHLOROETHYL BENZENE AND NUCLEAR CHLORINE SUBSTITUTION PRODUCTS THEREOF IN THE LIQUID PHASE WITH GASEOUS CHLORINE AT A TEMPERATURE BETWEEN -10* C. AND 30* C. IN THE PRESENCE OF IODINE AS CHLORINATION CATALYST, THE IODINE BEING USED IN AN AMOUNT OF ABOUT 0.12 TO 0.5% BY WEIGHT OF SAID BENZENOID COMPOUND TO PRODUCE ALPHA-CHLOROETHYL BENZENE PRODUCTS HAVING NUCLEAR CHLORO SUBSTITUTION AND CHLORO ADDITION GROUPS AND CONVERTING AT LEAST ONE CHLORO ADDITION PRODUCT IN THE REACTION MIXTURE TO THE CORRESPONDING CHLORINE SUBSTITUTED CHLOROETHYL BENZENE DERIVATIVE BY HEAT TREATMENT AT A TEMPERATURE BETWEEN 180 TO 300* C. 